Composition of matter



Patented Mar. 26, 1940 UNITED STATES PATENT OFFICE COIHPOSITION F MATTER No Drawing. Application March 10, 1939, Serial No. 261,092

8 Claims.

This application is a continuation in part of my pending application for patent Serial No. 211,037, filed May 31, 1938, which subsequently resulted in U. S. Patent No. 2,166,432, dated July 18, 1939.

My present invention consists of a new compound or composition of matter, consisting of a certain kind of complex amine derived by re action between (a) acid esters obtained by rein action between phthalated triricinolein, phthalated ricinoleic acid, or similar materials, and (b) simpler amines of the kind hereinafter described. I have found that said new compound is particularly adapted for use as a demulsifler in the resolution of crude oil emulsions, either alone, or in admixture with conventional demulsifying agents of a compatible type. It may also have uses in other arts that I have not yet investigated.

In order that the present application may be considered a complete disclosure of my invention, I deem it advisable to describe the raw materials entering into the manufacture of my new compound or composition of matter, as well as the method or procedure employed to produce said compound.

One can obtain or manufacture chemical compounds whose composition is indicated by the following formulas:

R.COO.C:H|

/NT OELOflL The compounds above described may be summarized by the following formula:

(R.c0o.0,Hl)..

(0H.C3H ),u

in which m represents the number 1 or 2, m represents the number 1 or 2, and m" represents the number 0 or 1, with the proviso that r n 3 However, the radical C2H4 which appears in the above formula may represent any similar radical, such as a CaHe radical, C4H8 radical, etc., a and therefore, the above formula may be rewritten:

where n represents a small whole number, preferably not over 10.

In the above group, T represents a hydrogen 15 atom, or a. non-hydroxy aliphatic hydrocarbon radical, such as a methyl, ethyl, propyl, amyl, or similar radical; or T may represent a non-hydroxy alicyclic radical, such as a cyclohexyl radical, or a non-hydroxy aralkyl radical, such as 20 a benzyl radical; or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid, such as acetic acid,

butyric acid, heptolc acid, or the like, all of which 25 are characterized by having less than 8 carbon atoms. The alkylol radical, prior to acylation, may be a hydroxy alicyclic or a hydroxy aralkyl radical, provided that the hydroxy radical is attached to the aliphatic residue of the aralkyl a0 radical.

In the above formula, R.COO represents the oxy-acyl or acid radical derived from the acid R.COOH. R.COOII represents any monobasic detergent-forming carboxy acid, such as a typical fatty acid or abietic acid or naphthenic acid. Typical fatty acids are those which occur in naturally occurring oils and fats, and. generallyhave eight or more carbon atoms and not over 32 carbon atoms. Common examples include oleic 0 acid, stearic acid, linoleic acid, linolenic acid, ricinoleic acid, erucic acid, palmitic acid, myristic acid, etc. These acids combine with alkali to produce soap or soap-like materials, and are commonly referred to as being monobasic detergent-forming carboxy acids. Blown oils (oxidized oils) are not included.

The alkylol radical previously referred to, prior to esterification, may be a hydroxy alicyclic or a hydroxy aralkyl radical, provided that the hy- 50 droxy radical is attached to the aliphatic residue of the aralkyl radical.

As to the amines above described, which happen to be tertiary amines, it may be well to point out that these may be formed readily by a 5,

reaction involving an ester of the selected detergent-iorming acid, for instance, a fatty acid ester, such as the glyceride, and a corresponding amine. This may be illustrated in the following manner:

Reference is made to co-pending. application for patent, Serial No. 180,993, filed December 21, 1937, by Melvin De Groote, Bernhard Keiser, and Charles M. Blair, Jr.

If triethanolamine, as employed in the above formula, is replaced by ethyl diethanolamine, then one would obtain one of the remaining types of tertiary amines illustrated. Reference is made to co-pending application for patent, Serial No. 206,903, filed May 9, 1938, by De Groote, Kaiser, and Blair, Jr., which subsequently resulted in U. 8. Patent No. 2,167,348.

In the remaining type oi material there is an amino hydrogen atom present. The manufacture of such material may be illustrated by the following reactions:

one need not resort to reactions of the kind previously described to produce secondary amines,

but one may employ the following type of reaction:

OILOsHo NE OEOe'B'a 3.0 03.0 R.O00 OsHo+ KK -o ILOOO OEOI 4 Oil-L053 NH 0H.O|H4

8 +C;H|(0H)| OH-CIHI Suitable primary and secondary amines which may be employed to produce materials of the kind above described include the following: diethanolamine, monoethanclamine, ethyl ethanolamine, methyl ethanolamine, propanolamine, dipropanolamine, propyl propanolamine, etc. Other examples include cyclohexylolamine, dicyclohexylolamine, cyclohexyl ethanolamine, cyclohexyl propanolamine, benzylethanolamine, benzylpropanolamine, pentanolamine, hexanolamine, octylethanolamine, octadecylethanoiamine, so

(13340013401! OIHIOOIHIOH CJHaOClHaOH r ormocimorr N 'OIHlOClHAOH N-Os iOH Such amines may serve as functional equivalents oi the previously described amines, and which are free from an ether linkage.

All of the amines of the kind above described and characterized by the formula:

in which m represents the number 1 or 2, 111. represents the number 1 or 2, and m" represents the number 0 or 1, with the proviso that m+m'+m"=3; and n represents a small whole number, preferably not over 10, have four common characteristics. In the first place, these amines are not quaternary ammonium bases or salts thereof. The expression quaternary ammonium" is properly and conventionally applied to compounds in which all four hydrogen atoms of the ammonium radical NH4 have been replaced by a hydrocarbon radical or oxy-hydrocarbon radical, as, for example, in trimethyl phenyl ammonium hydroxide.

Secondly, an important characteristic which must be recognized is that these amine compounds are not amides. It is to be noted that an amine formation involves a product in which there is a direct linkage between the carboxylic carbon atom and the nitrogen atom in the amine. This is not the case in the compounds employed as intermediate raw materials for production of the compounds used as demulsifying agents in the present process.

In the third place, it must be recognized that these compounds are derived only from basic amines. The word "basic" is employed to exclude amines having little or no basicity, such as the ordinary aromatic amines, or any amine having at least one aryl radical directly joined to the amino nitrogen atom. For this reason. these amine products which are herein contemplated as demulsifying agents in the resolution of petroleum emulsions, and which necessarily are characterized by freedom from any aryl groups as such, cannot be derived from aryl amines. They are derived solely from alkyl, alicyclic, or aralkyl amines having at least one hydroxyl group present.' It is true that in the arallgvl amines there is an aryl group present, but it is not directly attached to the nitrogen atom, as in the case of aryl amines, but, in fact, represents nothing more or less than a substituted alkylamine. For instance; I consider benzylamine as being the primary amine, phenmethyl amine.

Finally, it must be recognized that these materials have not lost any basicity in the forms of the esterifled amine, and that they exhibit all the properties of a basic amine, that is, they combine with water to form -a base, presumably a substituted ammonium compound, but not quaternary ammonium compound, insofar that there are always one, two-or three unsubstituted hydrogen atoms of the ammonium radical present. They combine with various acids to form salts. For example, they may be combined with acetic acid, hydrochloric acid, lactic acid, chloracetic acid, nitric acid, butyric acid, phosphoric acid, oxalic acid, or any suitable organic or inorganic acid, to form salts. It is understood that the reference in the specification and appended claims to the amines includes the basic form and the acid salts, as well as the amines themselves. The new compositions of matter herein described have great demulsifying properties, which are contributed, in part. by the amine, and it is immaterial whether the amine may be considered as being in any one of the following forms:

in which T represents the substituents for the amino hydrogen atoms of the parent ammonia from which all amines are hypothetically derived, and X simply represents the acid radical of any acid employed. This statement applies with equal force and effect to the final product, or composition of matter, which is also a basic amine of a more complex type.

Reference is again made to the formula which summarizes the various amines used as intermediate raw materials, viz.:

in which the characters have their previous significance. i

Attention is directed to the fact that where the substituted alkyl ardical OH.R..COO.C:H4 appears, a suitable non-aryl radical other than an aliphatic residue may serve as the functional equivalent; for instance, an alicyclic radical derived from a cyclohexyl radical, or an aralkyl radical derived from a benzyl radical. In other words, in the hereto appended claims reference to the CHI-Ian radical, as such, or as an alkyl radical or residue is intended in the broad sense to include the alicyclic radicals or residues, or the aralkyl radicals or residues which are the equivalent thereof. There is no intention to include an aromatic radical where there is a direct linkage between the aromatic nucleus and the amino hydrogen atom, for the reason that such products have little or no basicity, and do not have the characteristic properties of the amines previously described.

In indicating the various hydroxylated tertiary amines of the non-aryl type which may be employed to produce the amine herein described, it is desirable to indicate that amines of the type where a hydroxyl acyl radical replaces a hydro gen atom of the hydroxyl radical of the hydroxy tertiary amine, are not included within the broad class of hydroxy tertiary amines, unless there is another hydroxyl radical attached to the usual alkyl radical. For instance, if ethyl diethanolamine is treated with two moles of lactic acid, so as to form the dilactyl compound of the following formula:

then it is understood that such materials would not represent a hydroxy tertiary amine within the meaning or scope, as herein employed. It, on the other hand, triethanolamine were treated with lactic acid, so as to give monolacetyl triethanolamine of the following composition:

then such compound would be included, due to the presence of one or more hydroxyl radicals attached to the alkyl radicals.

Similarly, in indicating the various hydroxylated primary or secondary amines of the non-aryl type, which may be employed to produce the amine herein described, it is desirable to indicate that amines of the type where a hydroxy acyl radical replaces a hydrogen atom of the hydroxyl radical of a hydroxy primary or secondary amine, are not included within the broad class of hydroxy tertiary amines, unless there is another hydroxyl radical attached to the usual alkyl radical. For instance, if ethanolamine is treated with lactic acid, so as to form the lactyl derivative of the following formula:

then it is understood that such materials would not represent a hydroxy primary amine within the meaning or scope, as herein employed. The same would be true if the corresponding product derived from diethanolamine, provided that both hydroxy radicals had been esterified with lactic acid.

The manufacture of compounds from tertiary amines is relatively simple, because no precautions are necessary to prevent amidiflcation. The selected detergent-forming acid,or ester, as, for example, a fatty oil and the selected hydroxy tertiary amine, are mixed in suitable proportions and heated at some point above the boiling point of water, for instance, 110 0., and at a point below the decomposition point of the amine or the fatty oil, for instance, 180 C.. for a suitable period of time, such as two to eight hours. Mild agitation is employed. A catalyst, such as sodium oleate, sodium carbonate, caustic soda, etc., may be present in amounts of about one-half of 1% or less. It is noted that the fatty acids are employed in this instance in the form of an ester, to wit, the glyceride, although, as previously pointed out, other functional equivalents can be readily employed with equal facility. It is to be noted that the reactions above described do no take place to any appreciable extent, if the fatty acid has been converted into the soap or salt. Such salts are not functional equivalents. As previously indicated, an ester of abietic acid might be employed, if desired.

When, however, one is employing a hydroxy secondary amine, precautions must be taken so that one gets a substantial percentage of products derived by esteriiication, rather than amidification. Any suitable ester may be employed, but it is often most convenient to employ the glyceride of a fatty acid, for instance, triricinolein.

The selected glyceride and the selected bydroxy secondary amine are mixed in suitable proportions and heated at some point above the boiling point of the amine or fatty material, for instance, 180 C., for a suitable period of time, such as 4-24 hours. Mild agitation is employed. A catalyst, such as sodium oleate, sodium carbonate, caustic soda, etc., may be present in amounts of about or less. It is to be noted that the fatty acids are present in ester form and not in the form of the free acid, and thus there is no tendency to form the salt to any marked extent, and if conducted at the lower range of reaction temperatures, there is a decided tendency to form the esteriflcation products, rather than the amidiflcation products.

In order to illustrate suitable examples of the amines which may be used as intermediate raw materials, the following examples are given:

Intermediate amine-Emmple 1 Castor oil is employed. For sake of convenience, its molecular weight is considered as being 925. Commercial triethanolamine and castor oil in the proportion of one mole of castor oil and three moles of triethanolamine are heated to a temperature between 150-180" C. for two hours. Mild agitation is employed. The reaction product so produced may be used as such, or may be converted into the acetate or other suitable form.

7 Intermediate amine-Emmple 2 The same procedure is followed as in Intermediate amine Example 1, except that the ratio employed is two moles of the castor oil to three moles of triethanolamine.

Intermediate amine-Example 3 One mole of methyl naphthenate is reacted in the manner previously described with one mole of triethanolamine.

Intermediate amine-Example 4 Diethanolamine is substituted for triethanolamine in Example 3.

Intermediate amine-Example 5 Methyl abietate is substituted for methyl naphthenate in Examples 3 and 4 above.

Intermediate amine-Example 6 Olive oil is substituted for castor oil in Examples l and 2 above.

Intermediate amine-Example 7 Intermediate amine-Example 8 Cyclohexyl diethanolamine is substituted for triethanolamine in previous examples where tri-' ethanolamine has been employed, but subject to the same modification as indicated in Example 7 immediately proceding.

Intermediate amine-Example 9 Benzyl diethanolamine is substituted for triethanolamine in previous examples where it has been employed. (See modification noted in Examples 7 and 8 immediately above).

Having prepared the relatively simpler intermediate amine of the kind previously described, the second step in the preparation of the new composition of matter is to produce acid esters of the kind obtainable by reaction between polybasic carboxy acids, or their functional equivalents, such as the anhydrides, and hydroxylated fatty acids, esters, or the like.

The manufacture of this latter class of materlals is well known, because they have been used extensively in the manufacture of demulsiflers, plasticizers, and the like. The most readily available hydroxylated fatty body is castor oil, which consists of about 85% triricinolein. One of the most suitable dibasic acids is phthalic acid, because of its low cost, stability towards heat, etc. If triricinolein be indicated by the following formula:

A OHJLCO O. H

OHJLCOO. He

then reaction products of phthalic anhydride or phthalic acid may be indicated in the following manner, although for purposes of convenience, phthalic acid is not shown in the form of the C OO.R.COO.CHI

OHJLCOO. H

OHJLCOO. H:

COOH

HO.R.CO0. H

CO0.R.COO. Hr

OOH

COOH

COO.R.COO.CH:

D H000 CO0.R.COO. H

COO.R.COO. Ht

COOH

COOH

COO.R.C 00.011:

""-COO.R.COO. H

COO.R.COO.(LH1

A large number of related products immediately present themselves, for instance, esters derived by reaction with ricinoleio acid, hydroxystearic acid, dihydroxy stearic acid, and the like; or the corresponding esters derived from glycols or glycol ethers, such as ethylene glycol or diethylene glycol, which contain no free hydroxyl radicals attached to the glycol radical or residue. Similarly, one might have products derived from monohydric alcohols, for instance, ethyl ricinoleate, propyl ricinoleate, sodium ricinoleate, amylamine hydroxystearate, etc. It is intended to include blown oils. It is not the intention to include compounds of the type in which the hydroxyl radical is attached to a radical or residue which replaces a carboxylic hydrogen atom. For instance, it is not intended to include such materials as mono-olein, di-olein, monostearin, distearin, etc.

In the examples shown above, where the ester is polybasic, for instance, compounds of the type exemplified by C and D above, one might remove the acidity of one of the carboxylic hydrogen atoms or two of the carboxylic hydrogen atoms, in any feasible manner, that is, by neutralization with an alkali or by conversion into an ester involving reaction with a new kind of an alcohol, i. e., a monohydric, dihydric, trihydric, etc.

In the case of D above, two carboxylic hydrogens may be neutralized. In any event, however, the material derived by reactoin between a polybasic acid and its functional equivalent and a hydroxylated fatty material of the kind described, is characterized by the presence of at least one free carboxyl radical.

Where reference is made to ricinoleic acid, hydroxystearic acid, dihydroxystearic acid, a bydroxy fatty acid, and the like, it is evident that certain simple derivatives, such as the halogenated compounds, etc., are the obvious functional equivalents; for instance, chlorinated triricinolein. may be employed instead of triricinolein. Brominated ricinoleic acid might be employed instead of triricinolein. Brominated ricinoleic acid might be employed instead of ricinoleic acid. In these instances the hydroxylated fatty material, notwithstanding modifications of the kind indicated, still has the same functional properties as the unmodified hydroxylated fatty material, and thus acts in the same manner, as far as chemical reactions noted are concerned, and also as far as producing an effective demulsifying agent is concerned. In the hereto appended claims reference to a hydroxylated fatty material includes such obvious functional equivalents.

The polybasic acids which may be employed, including some having at least three carboxyl radicals, are phthalic, succinic, malic, fumaric, citric, maleic, adipic, tartaric, glutaric, diphenic, naphthalic, oxalic, etc.

As to the manufacture of materials of the kind described by reactions involving the 'polybasic carboxy acids, or their equivalent, reference is made to the following patents, although it is not intended to infer that such patents describe these materials exclusively. However, they make such reference to the type of reaction involved that a skilled chemist would readily note the description which is particularly pertinent to the type of material just referred to: U. S. Patent No. 1,976,602 to De Groote, Adams and Keiser,

dated October 9, 1934; and U. S. Patent No.'

1,977,146, to Roberts, dated October 16, 1934.

Composition of matter-Example 1 Castor oil is reacted with triethanolamine (see Example 1 in the previous group of intermediate amine examples) so as to produce a material corresponding to:

OH.R.COO.C:HA

oncinbi in which OH.R.COO represents the ricinoleic acid radical. One molecular weight of this material is reacted with three molecular weights of diphthalated triricinolein. (See Formula C above.) This is a conventional esterification reaction, and the materials are intimately mixed and heated at approximately 120l60 C., with constant agitation, until samples taken from the batch and analyzed show substantially complete disappearance of the hydroxyl value. A suitable solvent may be present, and water formed may be distilled 01f continuously during the esterification process. The solvent may remain behind in the final product, or be removed, if desired.

Composition of matter-Emample 2 OH.CH|/

is reacted with diphthalated. tririncolein in the same manner as indicated in Composition of matter Example 1.

Composition of matter-Example 3 The same procedure is followed as in Examples 1 and 2 above, except that the amine is derived by reaction in which cocoanut oil is substituted for tririclnolein in Intermediate amine Examples 1 and 2. In procedure of Example 1, two moles of diphthalated tririclnoleln are employed, whereas, in following Example 2, only one mole is employed.

Composition of matter-Example 4 The same procedure is followed as in Example 3, except that olive oil is substituted for cocoanut oil in the manufacture of the intermediate amines.

Composition of matter-Example 5 Dimaleated triricinolein is substituted for diphthalated triricinolein in Composition of matter Examples 1- 4, inclusive.

Composition of matter-Example 6 Dicitrated triricinolein is substituted for diphthalated triricinolein in Composition of matter Examples 1-4, immediately preceding.

Composition of matter-Example 7 Triphthalated triricinolein (see formula 'in Composition of matter Example 2 above) is substituted for diphthalated triricinolein in. Composition of matter Examples 1-4 immediately preceding.

Composition of matterE.1:ample 8 An intermediate amine is obtained by reaction between diethanolamine and castor oil.'so as to yield a product having one non-esterifled ethanol radical. This product is reacted with two moles of diphthalated triricinolein.

It should be noted that this particular product contains only two hydroxyl radicals available for esteriflcation per atom of nitrogen, and therefore, the proper adjustment in molecular proportions, as indicated, must be made. Insofar that some amidification may take place in following the directions in preparing the intermediate amine from diethanolamine, it is probably the safest procedure to determine the acetyl or hydroxyl value before reacting in molecular proportions with the acidic ester, so as to be certain to leave a carboiwl radical.

Composition of matter-Example 9 Monophthalated hydroiwstearic acid is substituted in the various previous examples. For instance, one may employ two moles of monophthalated hydroxystearic acid and one mole of the amine product of the kind indicated in Composition of matter Example 1, above.

Composition of matter-Example 10 Two moles of dihydroxystearic acid are to be treated with one mole of phthalic anhydride, so as to eliminate completely any free carboxyl ra'dicals attached to the phthalic anhydride or phthalic acid residue. Two moles of this compound so obtained are reacted with one mole of the intermediate amine of the kind described in Composition of matter Example 1, above.

Composition of matter-Example 11 Two moles of monophthalated hydroxystearic acid and one mole of the product derived from dlethanolamine and castor oil, characterized by the presence of one non-esterifled ethanol radical, are reacted in the same manner, as previously described.

Composition of matter-Example 12 Two moles of dihydroxystearic acid are treated with one mole of phthalic anhydride, so as to eliminate completely any free carboxyl radicals attached to the phthalic anhydride or phthalic acid residue. Two moles of this product so obtained are reacted with one mole of the product derived by esteriflcation of diethanolamine in the manner described in the Composition of matter example immediately preceding.

Attention is directed to the fact that the alblolamines are obtained in such a manner that they may be looked upon as being derivatives of dihydric alcohols. for instance, the chlorhydrin of the dihydric alcohol. as indicated in the following manner:

are available from glycerols, polyglycerols, and the like, as indicated by the following reaction:

types of reactions will produce secondary or tertiary amines and that the reaction is not limited to a combination with ammonia, but may take place with a combination of other primary or secondary amines, such as amylamine, diamylamine, cyclohexylamine, dicyclohexylamine, benzylamine, dibenzylamine, amylcyclohexylamine, etc.

This means that in the typeof material previously described, there is a wide variety of material, such as monoglycerylamine, diglycerylamine, monoglyceryl diethylamine, monoglyceryl dipropylamine, diglyceryl propylamine, triglycerylamine, etc., which are functional equivalents of the various amines previously described for reaction with tririclnoleln and the like. when such amines are employed instead of the radical -'CnH2n appearing in a compound, one would have in place thereof the radical -0H.CaHs; or, in case the hydroxyl radical of these --OH.CaHsradical had been removed by esterification with any available carboxyl, then the substituent which replaces the CnH2n radical might be indicated by the formula D.CaH5. All that has been said here in regard to functional equivalents will be perfectly obvious without further explanation to those skilled in the art. (See U. S. Patent No. 2,091,704 dated August 31, 1937, to Duncan and McAllister, and also U. S. PatentNo. 2,042,621, dated June 2, 1936, to Olin.)

Similarly, it is evident that where reference is made to phthalic acid, some simple derivative, such as chlorinated phthalic acid, brominated phthalic acid, methylated phthallc acid, or the like, would simply act as a functional equivalent. This applies not only to phthalic acid, but all the dibasic acids or polybasic acids enumerated.

Similarly, it is evident that there is no intention to differentiate between isomeric forms. One isomeric form may serve as well as another. Attention is particularly called to the last two examples above, which are characterized especially by the presence of a free carboxyl radical other than the carboxyl radical derived from dibasic acid. Needless to state, in the reaction between the ester derived by reaction between a polybasic carboxy acid material and a selected fatty material of the kind described, if there be a carboxyl radical attached to a fatty chain available for esterification, as well as a carboxyl attached to the dibasic acid, then, in such event, if there is sufllcient available hydroxyl radicals attached to the amine of the kind previously described, both types of carboxyl radicals, i. e., (a) a carboxyl radical attached to a polybasic carboxy acid residue; and (b) a carboxyl radical attached to a fatty acid residue may enter into the reaction. However, my experience is that the carboxyl radical attached to the polybasic carboxy acid residue is generally more reactive andenters into reaction in preference to the other type of carboxyl radical, although both reactions may take place simultaneously to at least a limited degree.

I desire to emphasize that any of the products obtained in the above examples, when employed as a demulsifier in the resolution of crude oil emulsions, may be used in the form of the amine by direct contact with an emulsion without contact with water. It may be contacted with water, i. e., in the form of a solution so as to produce in a greater or lesser degree the amine base. Furthermore, any of the products above described may be combined with a suitable acid. Acetic acid may be employed. Hydrochloric acid is particularly desirable. In some instances acids, such as oleic acid or naphthenic acid, may be employed to give a suitable salt. As previously pointed out, any carboxylic hydrogen atom may be replaced by a. suitable-metallic atom, or an organic radical derived from an alcohol or from an amine. All such ionizable hydrogen atom equivalents are considered as the functional equivalent of the ionizable hydrogen atoms themselves, and such neutralized forms are included in the scope of the appended claims as the equivalent of the acidic form. The expression fatty acid compound is employed to include the acid itself, as well as salts and esters thereof. It is realized that where a free carboxyl and a basic amine residue exists in the same molecule, there may be a tendency towards the formation of inner salts comparable to sulphanilic acid; but due to the size of the molecule involved, and perhaps for reasons of steric hindrance, I am not aware that such inner salts are formed.

Briefly, then, the composition of matter herein contemplated depends on a reaction involving a polybasic carboxy acid body or its functional equivalent, as described, and the complex amine of the kind described, in such a manner as to involve reactions other than salt formation. In other words, the complex amines are basic in nature, and therefore, could react with a polybasic acid to form a salt in a manner which, for sake of convenience, will be indicated by a somewhat simpler reaction, thus:

OOOH or [RtNH]0OC.T.COONB I desire to emphasize that the expressionpolybasic carboxy acid, as it appears in the claims, refers not only to the acid itself, but to any functional equivalent, such as the anhydride,

the acyl chloride, a salt form havingat least two free carboxyls, such as mono-sodium citrate, etc. It is also understood that in the hereto appended claims the nature of the final product is not limited to the form having a free carboxylic hydrogen, but that such free carboxylic hydrogen may actually be replaced by any functional equivalent of the kind previously described, for instance, a metallic atom, an ammonium radical, an amine radical, such as an amylamine radical, benzylamine radical, ethanolamine radical, diethanoiamine radical, triethanolamine radical, a hydrocarbon radical, such as an ethyl, methyl, propyl, or amyl radical, a radical derived from ethylene glycol, glycerol, or the like; a cyclohexyl radical, benzyl radical, etc. All such forms in which such ionizable hydrogen atom equivalent replaces an ionizable hydrogen atom, are obvious functional equivalents.

Attention is directed to the fact that the word amidiflcation" has been applied to the reaction involving the replacement of an amino hydrogen atom by an acyl radical without conventional limitation to a reaction involving ammonia. The replacement of the amino hydrogen atom of a primary amine or a secondary amine by an acyl radical has been considered as being amidification, rather than the formation of a substituted amide or the formation of an imide or substituted imide. Such obvious departure from conventional nomenclature has been for purposes of simplicity and to show the similarity between certain reactions.

It is desirable to emphasize again that in the hereto appended claims reference to a polybasic carboxy acid compound includes not only the acid itself, but also various salts and esters thereof. and also other functional equivalents, such as the anhydrides, acyl chlorides, etc. Similarly, in the hereto appended claims reference to a hydroxylated fatty acid compound includes not only the fatty acid itself, but also the salts and esters thereof, except esters of the kind in which there is a hydroxyl attached to the hydrocarbon radical derived from the esterifying alcohol; i. e., it is not intended toinclude esters such as monoricinolein, diricinolein, etc., characterized by the presence of a hydroxyl radical attached to the organic radical which replaces the ionizable hydrogen atom of the carboxy radical of the fatty acid. Furthermore, in the hereto appended claims, reference to the product derived by reaction between an acid ester of the kind previously described and an amine of the kind previously described, is meant to refer to such products in all its various modifications previously referred to, to wit, such instances where carboxylic hydrogen atoms appear as such, or have been replaced by metallic atoms, organic radicals derived from various alcohols, amine radicals, or residues, etc.; and as to the presence of any basic amine nitrogen atom, it may be in the amine form or in a salt form or in a base form, as, for example, obtainable by contact with water. The functional equivalents of all these variations have been pointed out previously and were readily comprehended; and the scope of the claims, in light of such obvious equivalents, requires no further discussion.

As to blown oils, blown fatty acids, polymerized oils, polymerized fatty acids, and other similar materials obtained by oxidation, it is understood that they may be reacted with the polybasic carboxy acids, such as phthalic acid or phthalic anhydride to produce an acidic ester; but it is not intended that they should be reacted with amines to produce the intermediate amine, which, in turn, is reacted with the acidic ester derived, in part, from a polybasic carboxy acid.

In considering the composition of matter herein disclosed, at least,'to the extent that theyare derived from basic diols, it is necessary to appreciate that such substances are not resins in the sense that such term is used to indicate materials which are obtained from the same raw materials combined in different proportions and under different conditions of reaction. The simplest resin formation may be exemplified by the reaction between ethylene glycol and phthalic acid. The product of such reaction may be indicated by the following formula:

on[clmooocoo] 11 In such resins n represents a fairly large whole number. It is obvious that if one hydroxyl of triethanolamine has been esteriiied with a monobasic carboxy acid, that the resultant product indicated, as previously stated, by the following formula, may conveniently be considered as a diol".

OHCDKGNCIHOOB Similarly, such a product can form a resin comparable to one obtained from the commonest diol, to wit, ethylene glycol, and would be indicated thus:

If ricinoleic acid be indicated thus:

OHRCOOH and the glyceride triricinolein be indicated thus:

OHLRCOO ormvcoo-mm on-n'coo it becomes obvious that phthalated recinoleic acid would be indicated thus:

noooGooorucoon and diphthalated triricinolein be indicated in the following manner :2'

COOH

OOOH

In a dlbasic acid such as phthalic acid and the like, where the two carboxyl groups are either attached to adjacent carbon atoms, or carbon atoms which are relatively close together, and where the distances from the carboxyl radical to the common carbon atom chain are substantially uniform, resinification takes place readily. In other words, in the product, as exemplified by the diol derived by esterifying a mole of triethanolamine with a mole of a fatty acid, the product reacts readily with phthalic anhydride under proper conditions to produce a resinous material as previously indicated. Such resinous material may be modified by introduction of a fatty acid,

so as to stop further growth by reacting with the available hydroxyl. Such material as a resin would be comparable to a modified special alkyd resin.

If, however, phthalic anhydride, as such, is not used in the free state, but instead, a state where one carboxyl has been united with a fatty body, such as phthalated triricinolein, phthalated ricinolein acid, or the like, as previously described,

then such materials, even though they are dibasic, do not react to produce resins, and do not build up molecules of a resinous nature in conjunction with basic diols, for various reasons, some of which are apparent and some of which are not. In the first place, steric hindrances possibly prevent random contact. In the second place, the basicity of the nitrogen atom tends to form inner salts. The space distances between carboxyl radicals becomes large in terms of intervening atoms. Since the alcoholic hydroxyl of ricinoleic acid is attached to the twelfth carbon atom, counting the carboxy atom as one, it means that in the radical indicated by R above there is a side chain having six more carbon atoms which may be an interfering group, even though it is not depicted. Finally, the molecular reactions really involve three dimension components, and the final product is of three dimensions. Chemical formulae as above employed are at the best limited to two dimensions. It is diillcult to contemplate such complex reaction of actual three dimensional combinations, based on structural formulae of two dimensions only. However, enough has been said in this discussion to enable one to realize that the compounds herein contemplated, particularly when derived from basic diols, should not be confused with resinous materials.

For convenience, in the present instance the expression diol" has been used in reference to the material derived by an esterincation of one hydroxyl triethanolamine or the like. Similarly.

the expression "trihydric will be conveniently used to indicate combinations that have at least three alcoholic hydroxyl radicals, and thus would include materials which actually have more than three; for instance, materials which have four or more hydroxyl radicals obtained, for instance, by derivatives of dihydroxy stearic acid, or from glyceryl amines, or both. Obviously, a polybasic carbon acid having more than two carbonyl radicals still acts as if it only had two carboxy radicals in such instances where one of such radicals has been rendered inactive by esteriflcation, or salt formation, as in the instance of monosodium salt of citric acid, to which previous reference has been made.

The method of using the herein described new compound or composition of matter to resolve a petroleum emulsion of the water-in-oil type, is clearly disclosed in my parent application Serial No. 1. flied May 31, 1938 which has (ORG-i n) n' in which 3.000 represents the oxy-acyl radical derived from a detergent-forming monocarboxy acid having not more than 32 carbon atoms; T represents a member of the class consisting of hydrogen atoms, hydrocarbon radicals and nonhydroxy acylated radicals obtained by replacing a hydrogen atom of the hydroxyl group of an almlol radical by the acyl radical of a monobasic carboxy acid having less than aicarbon atoms; n represents a small whole number which is less than 10; m represents the number 1 or 2; m represents the number 1 or 2, and m" represents the number 0 or 1, with the proviso that m-l-m'+m" equals 3; and (B) an acidic ester derived by reaction between a dibasic carboxy acid and a hydroxylated fatty acid compound; said fatty acid compound-being characterized by the absence of any hydroxy substituted hydrocarbon radical as a substituent for the hydrogen atom in the carboxy part of the hydron fatty acid radical, said acidic ester being characterized by the presence of at least one carboxyl radical.

2. The product resulting from an esteriilcation reaction between (A) an amine of the formula type in which R.CO0 represents the oxy-acyl radical derived from a detergent-forming monocarboxy acid having not more than 32 carbon atoms; T represents a member of the class consisting of hydrogen atoms, hydrocarbon radicals and non-hydroxy acylated radicals obtained by replacing a hydrogen atom of the hydroxyl group of an allqrlol radical by the acyl radical of a monobasic carboxy. acid having less than 8 carbon atoms; n represents a small whole number which is less than 10; m represents the number 1 or 2; m represents the number 1 or 2, and m" represents the number 0 or 1, with the proviso that m+ equals 3; and (B) an acidic ester derived by reaction between a dibasic carboiw acid and a hydroxylated fatty acid compound; said fatty acid compound being characterized by the absence of any hydroxy substituted hydrocarbon radical as a substituent for the hydrogen atom in the carboxyl part of the hydroxy fatty acid radical; said acidic ester being characterized by the presence of at least one carboxyl radical.

3. The product resulting from an esterification reaction between (A) an amine of the formula (0H.CnHla) in which R.COO represents the oxy-acyl radical derived from a detergent-forming monocarboxy acid having not more than 32 carbon atoms; and n is a small whole number less than 10; and (B) an acidic ester derived by reaction between a dibasic carboxy acid and a hydroxylated fatty acid compound; said fatty acid compound being characterized by the absence of any hydroxy substituted hydrocarbon radical as a substituent for the hydrogen atom in the carboxyl part of the hydroxy fatty acid radical; said acidic ester being characterized by the presence of at least one carboxyl radical.

4. The product resulting from an esteriiication reaction between (A) an amine of the formula typ (0 H C aHh) n' in which R.C00 represents the oxy-acyl radical derived from a detergent-forming monocarboxy acid having not more than 32 carbon atoms: 1:

represents a small whole number which is less than 10; m represents the number 1 or 2; m represents the number 1 or 2, with the proviso that m+m'=3; and (B) an acidic esterderived by reaction between a dibasic carboxy acid and a hydroxylated fatty acid compound; said fatty acid compound being characterized by the absence of any hydroxy substituted hydrocarbon radical as a substituent for the hydrogen atom in the carboxyl part of the hydroxy fatty acid radical; said acidic ester being characterized by the presence of at least one carboxyl radical.

5. The product resulting from an esteriflcation reaction between (A) an amine of the formula (0H.C:Hi)

in which R.COO is. an oxy-acyl radical derived from a fatty acid; and (B) an acidic ester derived by reaction between a dibasic carboxy acid and a hydroxylated fatty acid compound; said fatty acid compound being characterized by the absence of any hydroxy substituted hydrocarbon radical as a substituent for the hydrogen atom in the carboxyl part of the hydroxy fatty acid rad-- ical; said acidic ester being characterized by the presence of at lease one carboxyl radical.

6. The product resulting from an esterification reaction between (A) an amine of the formula typ (OH.C|Hc)| in which R.COO is an oxy-acyl radical derived from a fatty acid; and (B) an acidic ester derived by reaction between a dibasic carboxy acid and a hydroxylated fatty acid compound; said (OILCsHO in which R.COO is an oxy-acyl radical derived from a fatty acid; and (B) an acidic ester derived by reaction between phthalic anhydride and tricinolein; said ester being characterized by the presence of at least one free carboxyl radical.

8. The product resulting from an es teriiication reaction between (A) an amine oi the formula ime (ILOOOJJM in which R1200 is an oxy-acyl radical derived from a fatty acid; and (B) an acidic ester derived by reaction between phthaiic anhydride and tricinoiein: said ester being characterized by the presence of at least one tree cal-boxy] radical.

MELVIN DE GROO'I'E.

CERTIFICATE OF CORRECTION. Patent No; 2,1911 61411.. march 26, 19140 7 mzLvn; DE GROOTE.

It is hereby certified that error appears in the printed specification of the above umhered' patent requiring correction as follows: Page 3, sec- 'ond.co1umn, line 12, for "ard1cel"'read "radical"; line 51 for "monolacetyl" read --monolactyl--; page 8, first column, lines 26 to 28 in the last line rthe formula, for "c n occm" reed --c H ooc.R-- and that u said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

. sig a end sealed this 30th day or Jul A. D. 191m.

Henry .Van Ar'sdale,- I (Seal) Acting Conmissio'ner of Patents. 

